WO2012005545A2 - Procédé pour l'extraction économique de lithium à partir d'une solution comprenant du lithium - Google Patents

Procédé pour l'extraction économique de lithium à partir d'une solution comprenant du lithium Download PDF

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WO2012005545A2
WO2012005545A2 PCT/KR2011/005026 KR2011005026W WO2012005545A2 WO 2012005545 A2 WO2012005545 A2 WO 2012005545A2 KR 2011005026 W KR2011005026 W KR 2011005026W WO 2012005545 A2 WO2012005545 A2 WO 2012005545A2
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lithium
brine
magnesium
boron
calcium
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PCT/KR2011/005026
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English (en)
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WO2012005545A3 (fr
WO2012005545A4 (fr
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Uong Chon
Oh Joon Kwon
Jin Gun Sohn
Ki Hong Kim
Chang Ho Song
Gi Chun Han
Ki Young Kim
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Research Institute Of Industrial Science & Technology
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Priority to JP2013519573A priority Critical patent/JP5587500B2/ja
Priority to EP11803831.4A priority patent/EP2591130B1/fr
Priority to CN2011800394188A priority patent/CN103069022A/zh
Publication of WO2012005545A2 publication Critical patent/WO2012005545A2/fr
Publication of WO2012005545A3 publication Critical patent/WO2012005545A3/fr
Publication of WO2012005545A4 publication Critical patent/WO2012005545A4/fr
Priority to US13/736,143 priority patent/US8778289B2/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C01B25/308—Methods for converting an alkali metal orthophosphate into another one; Purification; Decolorasing; Dehydrating; Drying
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method of extracting lithium from a lithium bearing solution.
  • the application of lithium currently extends to diverse industries,including the rechargeable battery, glass, ceramic, alloy, lubricant, and pharmaceutical industries.
  • the lithium rechargeable battery has recently been receiving attention as a main power source for hybrid and electric cars, and the market for lithium rechargeable batteries for cars is expected to continue growing to approximately one-hundred times the conventional compact battery markets for cell phones and notebooks.
  • the main sources for the lithium could be minerals, brine and seawater. Although minerals such as spodumene, petalite and lepidolite contain relatively large amountsof lithium, ranging from approximately 1 to 1.5%, the extraction involves complicated processes such as floatation, calcining at a high temperature, grinding, acid mixing, extraction, purification, concentration and precipitation. These processes, require high energy consumption, are considered to be cost-ineffective, and the use of acids during the lithium extraction also causes environmental pollution.
  • lithium is currently extracted from brine produced from natural salt lakes, but salts such as Mg, Ca, B, Na, K, SO 4 are also dissolved in the brine.
  • the concentration of lithium contained in the brine ranges from approximately 0.3 to 1.5g/L, and lithium contained in the brine is usually extracted in the form of lithium carbonate having a solubility of about 13g/L. Even assumingthat lithium contained in the brine is completely converted to lithium carbonate, the concentration of lithium carbonate in the brine is limited to 1.59 to 7.95g/L (the molecular weight of Li 2 CO 3 is 74, and the atomic weight of Li is 7. If the concentration of lithium is multiplied by 5.3 (74 ⁇ 14 ⁇ .3), the concentration of lithium carbonate can be estimated). Since most of the lithium carbonate concentration is lower than the solubility of lithium carbonate, the extracted lithium carbonate re-dissolves,and thus there is a problem of the lithium extraction yield being extremely low.
  • the brine pumped from the natural salt lake was stored in evaporation ponds and subsequently naturally evaporated outdoors over a long period of time, for instance about one year, to concentrate the lithium by several tenfold. Then, the impurities such as magnesium, calcium, boron were precipitated in order to be removed, and the method required an amount greater than the solubility of lithium carbonate to precipitate.
  • Chinese Patent Pub. No. 1,626,443 describes a method of extracting lithium, wherein brine is evaporated and concentrated under solar heat, and the concentrate is subject to repeated electro-dialysis in order to obtain brine containing concentrated lithium with a low amount of magnesium.
  • a method of economical extraction of high purity lithium phosphate with high extraction yield from brine which does not require the processes of evaporation and concentration of the brine for a long period of time, by using lithium phosphate having low solubility may be provided.
  • a method of economical extraction of lithium from a lithium bearing solution by adding a phosphorous supplying material to the solution to precipitate lithium phosphate from the dissolved lithium is provided.
  • the phosphorous supplying material may be one selected from the group consisting of phosphorous, phosphoric acid, phosphate and a mixture thereof.
  • the concentration of the lithium phosphate may be 0.39g/L or more.
  • the concentration of lithium in the lithium bearing solution may be 0.1g/L or more. More specifically, the concentration may be 0.2g/L or more, or 0.5g/L or more. The concentration of 60g/L or more, however, may not be economical because a great amount of time is required for the high-enrichment of lithium.
  • the method may further comprise a step of extracting lithium phosphate by filtering the precipitated lithium phosphate from the lithium bearing solution.
  • the lithium bearing solution may be brine.
  • the brine may contain impurities including magnesium, boron, calcium, or a mixture thereof.
  • the method may further comprise a step of precipitating and removing impurities in the brine, including magnesium, boron, calcium, or a mixture thereof by adding a hydroxyl ion in the brine.
  • the step ofprecipitating lithium phosphate from dissolved lithium by adding a phosphorous supplying material may be performed at room temperature or higher.
  • the hydroxyl ion may be a negative ion of sodium hydroxide.
  • the step of precipitating and removing impurities in the brine, including magnesium, boron, calcium, or a mixture thereof by adding a hydroxyl ion in the brine may be a step of precipitating and removing impurities in the brine, including magnesium, boron and calcium, by adding a hydroxyl ion in the brine.
  • the step of precipitating and removing impurities in the brine, including magnesium, boron and calcium, by adding a hydroxyl ion in the brine may further comprise the steps of:(a) producing magnesium hydroxide from the magnesium by adding a hydroxyl ion in the brine; (b) absorbing boron inthe magnesium hydroxide to extract magnesium and boron by co-precipitating magnesium and boron; and (c) precipitating calcium by adjusting the pH of the filtrate from which magnesium and boron are removed to be at least 12.
  • the step of producing magnesium hydroxide from the magnesium by adding a hydroxyl ion in the brine may be a step of producing magnesium hydroxide from the magnesium by adding a hydroxyl ion while maintaining the pH of the brine to be in the range of 8.5 to 10.5.
  • the step of absorbing boron in the magnesium hydroxide to extract magnesium and boron by co-precipitatingmagnesium and boron may be performed by absorbing the boron in the brine including the magnesium hydroxide having a pH ranging from 8.5 to 10.5 inthe magnesium hydroxide to extract magnesium and boron by co-precipitating magnesium and boron.
  • the step of producing magnesium hydroxide from the magnesium by adding a hydroxyl ion in the brine, while maintaining the pH of the brine to be in the range of 8.5 to 10.5 by adding a hydroxyl ion in the brine, and the step of absorbing the boron in the brine including the magnesium hydroxide having apH ranging from 8.5 to 10.5 in the magnesium hydroxide to extract magnesium and boron by co-precipitatingmagnesium and boron may be performed simultaneously.
  • the step of precipitating lithium phosphate from dissolved lithium by adding a phosphorous supplying material may be followed by a step of filtering the precipitated lithium phosphate and extracting it in the form of a high purity powder.
  • thestep of precipitating calcium by adjusting the pH of the filtrate from which magnesium and boron are removed to be at least 12 may be a step of precipitating calcium hydroxide or calcium carbonate from calcium by adding hydroxyl ion, carbonate ion, or a mixture thereof.
  • lithium dissolved in the brine may be economically extracted as lithium with high extraction yield by precipitation using lithium phosphate having low solubility.
  • FIG. 1 is a graph depicting the surface charge change of magnesium hydroxide according to the pH of the brine.
  • FIG. 2 is a graph depicting the concentration change of magnesium ions in the filtrate relative to the NaOH addition amount.
  • FIG. 3 is a graph depicting the concentration change of boron ions in the filtrate relative to the NaOH addition amount.
  • FIG. 4 is a graph depicting the concentration change of lithium ions in the filtrate relative to the NaOH addition amount.
  • FIG. 5 is a graph depicting the concentration change of calcium ions in the filtrate relative to the NaOH addition amount.
  • FIG. 6 is a graph depicting the concentration of lithium relative to the reaction time when lithium phosphate is precipitated from lithium.
  • FIG. 7 is a graph depicting the concentration of lithium relative to the reaction time and temperature when lithium phosphate is precipitated from lithium.
  • FIG. 8 is a graph depicting the concentration of lithium phosphate in the filtrate relative to the reaction time when lithium carbonate is precipitated from lithium.
  • a method of economical and efficient extraction of lithium from a lithium bearing solution by adding a phosphorous supplying material to the solution to precipitate lithium phosphate instead of lithium carbonate from the dissolved lithium may be provided.
  • lithium carbonate Li 2 CO 3
  • the solubility of lithium phosphate (Li 3 PO 4 ), however, is approximately 0.39g/L, which is relatively lower than that of lithium carbonate. Accordingly, it is possible to extract even a small concentration of 0.5g/L or1.5g/L of lithium dissolved in the lithium bearing solution, such as brine, which can be precipitated and separated into lithium phosphate in a solid state by adding a phosphorous supplying material in the lithium bearing solution.
  • the concentration of lithium in the lithium bearing solution may be 0.1g/L or more. More specifically, the concentration may be 0.2g/L or more, or 0.5g/L or more. The concentration of 60g/L or more, however, may not be economical because a great amount of time is required for the high-enrichment of lithium.
  • the phosphorous supplying material selected from the group consisting of phosphorous, phosphoric acid, phosphate, and a mixture thereof is added to the lithium bearing solution to produce lithium phosphate.
  • the concentration i.e., the dissolved concentration in the lithium bearing solution
  • the concentration should be 0.39g/L or greater.
  • the phosphorous supplying material is a compound capable of altering the pH of the lithium bearing solution (e.g., phosphoric acid)
  • hydroxide ions can be concurrently used to prevent the precipitated lithium phosphate from re-dissolving once the pH of the solution decreases.
  • the phosphate may be, for example, but is not limited thereto, potassium phosphate, sodium phosphate, and ammonium phosphate.
  • the ammonium may be (NR 4 ) 3 PO 4 , wherein R is independently a hydrogen, a heavy hydrogen, a substituted or unsubstituted C1-C10 alkyl group, but not limited thereto.
  • the phosphate may be, for example, but is not limited thereto, mono-potassium phosphate, di-potassium phosphate, tri-potassium phosphate, mono-sodium phosphate, di-sodium phosphate, tri-sodium phosphate, aluminum phosphate, zinc phosphate, poly-ammonium phosphate, sodium-hexa-meta-phosphate, mono-calcium phosphate, di-calcium phosphate, and tri-calcium-phosphate.
  • the phosphorous supplying material may be water-soluble. In the case the phosphorous supplying material is water-soluble, the reaction with lithium contained in the lithium bearing solution may easily occur.
  • the precipitated lithium phosphate may be extracted by filtering the lithium bearing solution.
  • the method of economical extraction of lithium from a lithium bearing solution by adding a phosphorous supplying material to the solution to precipitate lithium phosphate from the dissolved lithium may be performed at room temperature. More specifically, the temperature may be more than 20°C, 30°C, 50°Cor 90°C.
  • room temperature is not limited to a definite temperature, and it is construed to mean a temperature without the application of external energy. Accordingly, the room temperature may vary depending on time and place.
  • a step of removing impurities in the brine, including magnesium, boron or calcium, by adding a hydroxyl ion in a lithium bearing solution (e.g., brine) followed by precipitating may be included.
  • the hydroxyl ion may be, for example, but is not limited thereto, sodium hydroxide, potassium hydroxide, ammonium hydroxide.
  • the ammonium may be (NR 4 ) 3 OH, wherein R is independently a hydrogen, a heavy hydrogen, a substituted or unsubstituted C1-C10 alkyl group, but is not limited thereto.
  • the hydroxide may be an anion of sodiumhydroxide.
  • the hydroxyl ion may be an anion of hydroxide salt produced as a by-product during the extraction of lithium, because the cation of hydroxide salt has high solubility.
  • the step of precipitating and removing impurities in the brine, including magnesium, boron or calcium, by adding a hydroxyl ion in the lithium bearing solution may be a step of precipitating and removing impurities in the brine, including magnesium, boron and calcium, by adding a hydroxyl ion in the brine.
  • the step of precipitating and removing impurities in the brine, including magnesium, boron or calcium, by adding a hydroxyl ionin the brine may further comprise the steps of: (a) producing magnesium hydroxide from the magnesium by adding a hydroxyl ion in the brine; (b) absorbing boron in the magnesium hydroxide to extract magnesium and boron by co-precipitatingmagnesium and boron; and (c) precipitating calcium by adjusting the pH of the filtrate from which magnesium and boron are removed to be at least 12.
  • the step of (a) producing magnesium hydroxide from the magnesium by adding a hydroxyl ion in the brine and the step of (b) absorbing boron in the magnesium hydroxide to extract magnesium and boron by co-precipitating magnesium and boron may be performed individually or concurrently.
  • steps (a) and (b) may be performed simultaneously, whereas the steps may be performed separately if the amount of magnesium produced is insufficient.
  • the magnesium may be produced as magnesium hydroxide by adding a hydroxyl ion (e.g.,NaOH) to a lithium bearing brine including magnesium, boron, and calcium.
  • a hydroxyl ion e.g.,NaOH
  • a lithium bearing brine including magnesium, boron, and calcium.
  • the pH of the brine with the added hydroxyl ion (e.g., NaOH) may be adjusted to be between 8.5 and 10.5 and subsequently, the co-precipitation of magnesium and boron may be possible by absorbing boron in the magnesium hydroxide.
  • the steps may be performed concurrently.
  • magnesium dissolved in the brine may be precipitated as magnesium hydroxide by adding a hydroxyl ion (e.g., NaOH).
  • a hydroxyl ion e.g., NaOH
  • Magnesium hydroxide is characterized in having a low solubility of 0.009g/L, and has a tendency to easily precipitate in a basic solution having a pH of 8 or higher.
  • boron e.g., boron ions
  • boron ions may be absorbed on the surface of the produced magnesium hydroxide to co-precipitate magnesium and boron.
  • the surface charge of the magnesium hydroxide can be utilized.
  • the surface charge of the magnesium hydroxide is greatly influenced by the pH of the solution.
  • the boron ions existing in the form of a negative ion such as H 2 BO 3 - or HBO 3 2-
  • the surface charge of the magnesium hydroxide is negative, however, the negatively charged boron ions arenot absorbed in the magnesium hydroxide.
  • a hydroxyl ion e.g., NaOH
  • a hydroxyl ion e.g., NaOH
  • a hydroxyl ion e.g.,NaOH
  • boron e.g.,boron ions
  • an additional hydroxyl ion e.g., NaOH
  • an additional hydroxyl ion may be added to the filtrate to adjust the pH to be between 8.5 and 10.5 and subsequently precipitate the remaining magnesium and boron.
  • hydroxyl ion e.g., NaOH
  • the pH of the brine is not likely to be maintained at between 8.5 and 10.5, and thus the co-precipitation efficiency of magnesium and boron is likely to drop as well, resulting in the loss of lithium.
  • Calcium may be precipitated by adding a hydroxyl ion or carbonate ion (e.g., NaOH, carbonate, or a mixture thereof) to the filtrate from which magnesium and boron are extracted to adjust the pH to be 12 or higher.
  • a hydroxyl ion or carbonate ion e.g., NaOH, carbonate, or a mixture thereof
  • calcium hydroxide or carbonate hydroxide may be precipitated.
  • the filtration step to separate the precipitated magnesium hydroxide absorbed with the boron from the brine is omitted, and the pH is adjusted to be 12 or higher to eliminate calcium, the surface charge of magnesium hydroxide would be converted to negative,because the pH of the brine deviates from the range of 8.5 and 10.5.
  • the boron absorbed inthe magnesium hydroxide will be desorbed, and instead, positive lithium ions will be absorbed, causing both the loss of lithium and a decrease in the boron extraction yield.
  • the calcium hydroxide and the calcium carbonate having very lowsolubility, are easily precipitated when the pH is 12 or higher. Thus, it is preferable to maintain the pH of the filtrate to be 12 or higher.
  • a mixture of an alkali and carbonate can be added.
  • the alkali is selected from the group consisting of NaOH, KOH, Ca(OH) 2 , NH 4 OH, R 4 NOH ⁇ 5H 2 0 and a mixture thereof, wherein R is independently a C1-C10 alkyl group, such as, methyl, ethyl, propyl or butyl.
  • alkali e.g., NaOH
  • a significant amount of alkali e.g., NaOH
  • the pH could be economically maintained to be at least 12 even if the amount of alkali could be relatively reduced.
  • the carbonate is selected from the group having high solubility consisting of Na 2 CO 3 , K 2 CO 3 , and a mixture thereof, and sodium and potassium included in the carbonate are dissolved in the filtrate.
  • the precipitated calcium hydroxide or calcium carbonate is separated from the remaining filtrate, and subsequently calcium is extracted.
  • a phosphate supplying material may be added to the remaining filtrate from which the impurities are removed to precipitate lithium phosphate from lithium contained in the brine.
  • the step of precipitating lithium phosphate from the lithium bearing brine may be performed at room temperature or above, or at 40°Cor above. More specifically, the step may be performed at 50°Cor above, 60°Cor above, 70°Cor above, 80°Cor above, or 90°Cor above.
  • the phosphorous supplying material may be selected from the group consisting of phosphorous, phosphoric acid, phosphate, and a mixture thereof.
  • the concentration i.e., the dissolved concentration in the lithium bearing solution
  • the concentration should be 0.39g/L or greater.
  • the phosphate may be, for example, but is not limited thereto, potassium phosphate, sodium phosphate, and ammonium phosphate.
  • the ammonium may be (NR 4 ) 3 PO 4 , wherein R is independently a hydrogen, a heavy hydrogen, a substituted or unsubstituted C1-C10 alkyl group, but not limited thereto.
  • the phosphate may be, for example, but is not limited thereto, mono-potassium phosphate, di-potassium phosphate, tri-potassium phosphate, mono-sodium phosphate, di-sodium phosphate, tri-sodium phosphate, aluminum phosphate, zinc phosphate, poly-ammonium phosphate, sodium-hexa-meta-phosphate, mono-calcium phosphate, di-calcium phosphate, and tri-calcium-phosphate.
  • the phosphorous supplying material may be water-soluble. In the case the phosphorous supplying material is water-soluble, the reaction with lithium contained in the lithium bearing solution may easily occur.
  • the filtrate is calcinatedfor 10 to 15 minutes at room temperature, or at a temperature range of 40-200°C, 50-200°C, 60-200°C, 70-200°C, 80-200°C, or 90-200°C.
  • the step of extracting the precipitated lithium phosphate filtered from the filtrate may be performed.
  • the extracted lithium phosphate may be washed to obtain high purity lithium phosphate powder.
  • NaOH was added to brine containing magnesium ions 20,000ppm, boron ions 900ppm, calcium ions350ppm, and lithium ions 900ppm to precipitate magnesium hydroxide. While adjusting the pH of the brine, the surface charge of the precipitated magnesium hydroxide was measured. The results are shown in FIG. 1.
  • the surface charge of the magnesium hydroxide was maintained with a positive charge when the pH range of the NaOH added brine was between 8.5 and 10.5. Accordingly, the boron ionswith a negative charge were easily absorbed on the magnesium hyrdroxide, and the positively charged lithium ions were prevented from being absorbed. This minimized the loss of lithium, and efficiently extracted both magnesium and boron from the brine at the same time.
  • magnesium hydroxide was precipitated from the brine containing magnesium ions20,000ppm, boron ions 900ppm, calcium ions 350ppm, and lithium ions900ppm. Subsequently, a filtration was performed to separate the precipitated magnesium hydroxide from the brine. The filtrate was collected to measure the amount of magnesium, boron and lithium. The results are shown in FIGs.2, 3, and 4, respectively.
  • the amount of boron ions dissolved in the brine initially decreased as the amount of NaOH added increased. This may be explained by the fact that the pH change could be insignificantly affected by the addition of NaOH in the beginning, and the surface charge of the magnesium hydroxide precipitated from the brine having a pH value of 10.5 or lower had a positive charge. Thus, the negatively charged boron ions present in the filtrate were precipitated while adsorbed on the surface of the magnesium hydroxide.
  • the amount of lithum ions present in the filtrate were initially not influenced by the addedamount of NaOH. This could be explained by the fact that the positively charged lithium ionsexisting in the lithium bearing solution were not absorbed inthe magnesium hydroxide because the surface charge of magnesium hydroxide had a positive charge in the beginning. If an excessive amount of NaOH was added, however, the pH of the brine surpassed 10.5. Then, the surface charge of the magnesium hydroxide was converted to a negative charge and the negatively charged boron ions werenot absorbed to the surface. Consequently, the concentration of boron ionsexisting in the filtrate dramatically increased. On the contrary, the concentration of positively charged lithium ions existing in the filtrate rapidly decreased as the lithium ions were absorbed to the surface of the magnesium hydroxide.
  • NaOH wasadded to the brine containing magnesium ions 20,000ppm, boron ions900ppm, calcium ions 350ppm, and lithium ions 900ppm to precipitate calcium hydroxide from the solution containing calcium ions. Subsequently, a filtration was performed to separate the precipitated calcium hydroxide from the brine. The resulting filtrate was collectedto measure the amount of calcium. The result is shown in FIG. 5.
  • the pH of the lithium bearing solution is at least 12 in order to enhance the extract yield of the calcium ions from the brine.
  • the pH of the brine was prematurely adjusted to be at least 12 in the beginning, the surface charge of the precipitated magnesium hydroxide had a negative charge. This preventedthe absorbance of the boron ions and caused the loss of lithium due to the absorbance of positively charged lithium ions.
  • the pH of the brine Prior to extracting calcium by adding NaOH, the pH of the brine was adjusted to be between 8.5 and 10.5 so that the magnesium hydroxide having a positive charge was precipitated to prevent the absorbance of the lithium ions. Once the boron ions were absorbed, the simultaneous extraction of magnesium and boron was performed. Then, the pH of the remaining filtrate from which magnesium and boron were extracted wasadjusted to be at least 12 to precipitate the calcium hydroxide from calcium.
  • the impurities including magnesium, calcium and boron, were removed from the brine, and 7.217g/L of sodium phosphate was added to the remaining filtrate dissolved with the concentration of lithium ions being 0.917g/L.
  • the filtrate was maintained to be reacted for 15 to 60 minutes, while elevating the temperature to 90°C.
  • the concentration of lithium in the filtrate initially decreased dramatically when sodium phosphate was added to the brine. After the reaction time passed 15 minutes, the concentration of lithium in the filtrate came to be below 50 mg/L. This indicated that more than 95% of lithium dissolved in the brine was precipitated and separated as lithium phosphate.
  • lithium phosphate Since the solubility of lithium phosphate is approximately 0.39g/L, which is much lower than the solubility of lithium carbonate, adding a material including phosphorous, such as sodium phosphate, in the brine precipitated lithium phosphate in the form of solid from a small amount of lithium dissolved in the brine.
  • a material including phosphorous such as sodium phosphate
  • the lithium extraction yield was more than 90% after the reaction time of 10 minutes, and the yield was more than 95% after 15 minutes.
  • the impurities including magnesium, calcium and boron, were removed from the brine, and 7g/L of sodium carbonatewas added to the remaining filtrate dissolved with the concentration of lithium ions being 0.917g/L.
  • the filtrate was maintained to be reacted for 15 to 60 minutes, while elevating the temperature to 90°C
  • lithium phosphate having a low solubility By precipitating lithium dissolved in the brine by using lithium phosphate having a low solubility, the processes of evaporation as well as concentration of brine are not required, and the economical extraction of lithium with high extraction yield, while minimizing the loss of lithium, may be possible.

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Abstract

La présente invention concerne un procédé d'extraction de lithium à partir d'une solution contenant du lithium. Plus spécifiquement, la présente invention concerne un procédé économique d'extraction de lithium à partir d'une solution comportant du lithium en ajoutant un matériau source de phosphore à la solution pour précipiter le phosphate de lithium à partir du lithium dissous.
PCT/KR2011/005026 2010-07-09 2011-07-08 Procédé pour l'extraction économique de lithium à partir d'une solution comprenant du lithium WO2012005545A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2013519573A JP5587500B2 (ja) 2010-07-09 2011-07-08 リチウム含有溶液からリチウムを抽出する方法
EP11803831.4A EP2591130B1 (fr) 2010-07-09 2011-07-08 Procédé pour l'extraction économique de lithium à partir d'une solution comprenant du lithium
CN2011800394188A CN103069022A (zh) 2010-07-09 2011-07-08 从含锂溶液中经济地提取锂的方法
US13/736,143 US8778289B2 (en) 2010-07-09 2013-01-08 Method for economical extraction of lithium from solution including lithium

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20100066391 2010-07-09
KR10-2010-0066391 2010-07-09
KR10-2010-0124089 2010-12-07
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US9598291B2 (en) 2012-04-05 2017-03-21 Posco Method for manufacturing lithium hydroxide and method using same for manufacturing lithium carbonate
US9994931B2 (en) 2012-07-31 2018-06-12 Posco Method for extracting lithium from solution containing lithium
CN102815680A (zh) * 2012-08-14 2012-12-12 焦作氟多凯工业有限公司 一种利用含锂废液生产磷酸锂的方法
CN104884648A (zh) * 2012-12-21 2015-09-02 浦项产业科学研究院 从含锂溶液中提取锂的方法
CN104884648B (zh) * 2012-12-21 2019-01-15 浦项产业科学研究院 从含锂溶液中提取锂的方法
US11806641B2 (en) 2016-11-14 2023-11-07 Lilac Solutions, Inc. Lithium extraction with coated ion exchange particles
US11794182B2 (en) 2017-08-02 2023-10-24 Lilac Solutions, Inc. Lithium extraction with porous ion exchange beads
US11253848B2 (en) 2017-08-02 2022-02-22 Lilac Solutions, Inc. Lithium extraction with porous ion exchange beads
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US11339457B2 (en) * 2020-01-09 2022-05-24 Lilac Solutions, Inc. Process for separating undesirable metals
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PT2591130T (pt) 2017-08-01
JP5587500B2 (ja) 2014-09-10
EP2591130A4 (fr) 2015-08-19
WO2012005545A3 (fr) 2012-04-26
CL2013000061A1 (es) 2013-07-19
US8778289B2 (en) 2014-07-15
CN103069022A (zh) 2013-04-24
US20130129586A1 (en) 2013-05-23
AR082147A1 (es) 2012-11-14
WO2012005545A4 (fr) 2012-06-14
JP2013535573A (ja) 2013-09-12
EP2591130A2 (fr) 2013-05-15
CN107012339A (zh) 2017-08-04
EP2591130B1 (fr) 2017-05-03

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